Oxidation‐Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H₂O₂

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(9)

Published: Dec. 30, 2022

The full reaction photosynthesis of H2 O2 that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization overcome complex reaction-process anthraquinone-oxidation. Here, a kind oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through covalent-coupling tetrathiafulvalene (photo-oxidation site) benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency photo-redox sites enables generation . Specifically, record-high yield (TTF-BT-COF, ≈276 000 μM h-1 g-1 ) for achieved among porous crystalline photocatalysts. This first work design COFs , might extend scope in production.

Language: Английский

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Confining Ti-oxo clusters in covalent organic framework micropores for photocatalytic reduction of the dominant uranium species in seawater

Chem, Journal Year: 2023, Volume and Issue: 9(11), P. 3172 - 3184

Published: July 11, 2023

Language: Английский

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Structural Regulation of Photocatalyst to Optimize Hydroxyl Radical Production Pathways for Highly Efficient Photocatalytic Oxidation

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(3)

Published: Oct. 22, 2023

Ring-opening of phenol in wastewater is the pivotal step photocatalytic degradation. The highly selective generation catalytical active species (•OH) to facilitate this process presents a significant scientific challenge. Therefore, novel approach for designing photocatalysts with single-atom containment metal-covalent organic frameworks (M-COFs) proposed. selection imine-linked COFs containing abundant N and O-chelate sites provides solid foundation anchoring metal atom. These dispersed atom possess rapid accumulation transfer capabilities photogenerated electrons, while periodic π-conjugated structure 2D-COFs establishes an effective platform. Additionally, Lewis acid properties imine bonds can enhance adsorption capacity toward gases base properties, such as O

Language: Английский

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Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H₂O₂ Photosynthesis Coupled with Biomass Valorization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 7, 2023

H2 O2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize production of value-added products. Here, a series COFs (i.e. Cu3 -BT-COF, -pT-COF and TFP-BT-COF) regulated redox molecular junctions have been prepared to study furfuryl alcohol (FFA) photo-oxidation furoic acid (FA). The FA generation efficiency -BT-COF was found be 575 mM g-1 (conversion ≈100 % selectivity >99 %) rate reach up 187 000 μM , which is much higher than -pT-COF, TFP-BT-COF its monomers. As shown by theoretical calculations, covalent coupling Cu cluster thiazole group promote charge transfer, substrate activation FFA dehydrogenation, thus boosting both kinetics increase efficiency. This first report about for valorization, might facilitate exploration porous-crystalline catalysts in this field.

Language: Английский

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Constructing Oxygen‐Related Defects in Carbon Nanodots with Janus Optical Properties: Noninvasive NIR Fluorescent Imaging and Effective Photocatalytic Therapy

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(35)

Published: May 22, 2023

Noninvasive fluorescence (FL) imaging and high-performance photocatalytic therapy (PCT) are opposing optical properties that difficult to combine in a single material system. Herein, facile approach introducing oxygen-related defects carbon dots (CDs) via post-oxidation with 2-iodoxybenzoic acid is reported, which some nitrogen atoms substituted by oxygen atoms. Unpaired electrons these rearrange the electronic structure of oxidized CDs (ox-CDs), resulting an emerging near-infrared (NIR) absorption band. These not only contribute enhanced NIR bandgap emission but also act as trappers for photoexcited promote efficient charge separation on surface, leading abundant photo-generated holes ox-CDs surface under visible-light irradiation. Under white LED torch irradiation, oxidize hydroxide hydroxyl radicals acidification aqueous solution. In contrast, no detected solution 730 nm laser indicating noninvasive FL potential. Utilizing Janus ox-CDs, vivo sentinel lymph nodes around tumors photothermal tumor PCT demonstrated.

Language: Английский

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5‐Hydroxymethylfurfural and its Downstream Chemicals: A Review of Catalytic Routes

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(37)

Published: May 29, 2024

Abstract Biomass assumes an increasingly vital role in the realm of renewable energy and sustainable development due to its abundant availability, renewability, minimal environmental impact. Within this context, 5‐hydroxymethylfurfural (HMF), derived from sugar dehydration, stands out as a critical bio‐derived product. It serves pivotal multifunctional platform compound, integral synthesizing various chemicals, including furan‐based polymers, fine biofuels. The high reactivity HMF, attributed highly active aldehyde, hydroxyl, furan ring, underscores challenge selectively regulating conversion obtain desired products. This review highlights research progress on efficient catalytic systems for HMF synthesis, oxidation, reduction, etherification. Additionally, it outlines techno‐economic analysis (TEA) prospective directions production chemicals. Despite significant catalysis research, certain process routes demonstrating substantial economics, with key indicators surpassing petroleum‐based products, gap persists between fundamental large‐scale industrialization. is lack comprehensive engineering bio‐based making commercialization distant goal. These findings provide valuable insights further field.

Language: Английский

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Modulated Connection Modes of Redox Units in Molecular Junction Covalent Organic Frameworks for Artificial Photosynthetic Overall Reaction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(42), P. 23167 - 23175

Published: Oct. 11, 2023

The precise tuning of components, spatial orientations, or connection modes for redox units is vital gaining deep insight into efficient artificial photosynthetic overall reaction, yet it still hard achieve heterojunction photocatalysts. Here, we have developed a series molecular junction covalent organic frameworks (COFs) (M-TTCOF-Zn, M = Bi, Tri, and Tetra) reaction. between TAPP-Zn multidentate TTF endows various water photo-oxidation (multidentate TTF) CO2 photoreduction (TAPP-Zn) centers that can serve as desired platforms to study the possible interactions centers. Notably, Bi-TTCOF-Zn exhibits high CO production rate 11.56 μmol g-1 h-1 (selectivity, ∼100%), which more than 2 6 times higher those Tri-TTCOF-Zn Tetra-TTCOF-Zn, respectively. As revealed by theoretical calculations, facilitates uniform distribution energy-level orbitals, faster charge transfer, stronger *OH adsorption/stabilization ability Tetra-TTCOF-Zn.

Language: Английский

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Flexible Units Induced Three-Dimensional Covalent Organic Frameworks with a Heteromotif Molecular Junction for Photocatalytic H₂O₂ Production

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3778 - 3787

Published: Feb. 22, 2024

In recent years, significant progress has been achieved in the field of three-dimensional covalent organic frameworks (3D COFs). However, there is still a great challenge to use flexible building units synthesize high-connectivity 3D COFs. this work, we showed that [6 + 3] COFs could be constructed by inducing highly planar blocks from C3 antitriangular prismed blocks. Herein, two with spn topology based on cyclotriphosphazene were and denoted as TAA/TAB-CTP-COF, their redox ability photophysical features can finely regulated coupled functional group, such benzene triazine groups. As result, heteromotif molecular junction TAA-CTP-COF fully exposed active sites high photocatalytic production hydrogen peroxide (H2O2) yield 1041 μM h–1 without any additional photosensitizers, scavengers, or cocatalysts. Furthermore, presence an electron donor, rate H2O2 reach up 2221 h–1, exhibiting one best performances for crystalline materials. This work showcases potential using highlights versatility efficacy metal-free solar energy conversion.

Language: Английский

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Redox Molecular Junction Metal‐Covalent Organic Frameworks for Light‐assisted CO₂ Energy Storage

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: March 28, 2024

Abstract Visible‐light sensitive and bi‐functionally favored CO 2 reduction (CRR)/evolution (CER) photocathode catalysts that can get rid of the utilization ultraviolet light improve sluggish kinetics is demanded to conquer current technique‐barrier traditional Li‐CO battery. Here, a kind redox molecular junction sp c metal‐covalent organic framework (i.e. Cu 3 ‐BTDE‐COF) has been prepared through connection between BTDE serve as efficient catalyst in light‐assisted ‐BTDE‐COF with redox‐ability, visible‐light‐adsorption region, electron‐hole separation ability endows excellent round‐trip efficiency (95.2 %) an ultralow voltage hysteresis (0.18 V), outperforming Schiff base COFs ‐BTDA‐COF ‐DT‐COF) majority reported catalysts. Combined theoretical calculations characterizations, integration centers, thiazole cyano groups possess strong adsorption/activation Li + interaction/diffusion boost CRR/CER related battery property.

Language: Английский

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COFs‐Based Metal‐Free Heterojunctions for Solar‐to‐Chemical Energy Conversion

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(49)

Published: Aug. 17, 2024

Abstract Covalent organic frameworks (COFs) are a promising class of polymers with the merits robust framework, ultrahigh porosity, and molecularly precise backbones, which reveals great potential for solar‐to‐chemical energy conversion in context mitigating environmental crises. However, photochemical activities individual COFs not as desired, primarily due to their limited light absorption, insufficient dissociation photogenerated excitons readily recombined carriers. Recently, COFs‐based metal‐free heterojunctions synergistic effects provide feasible route boost photocatalytic activity more environmentally friendly cost‐competitive manners. Herein, it is first systematically overview advances from heterojunction types, heterointerfaces interactions, primary design mechanisms. Then, typical photocatalysts (e.g., g‐C 3 N 4 ‐COFs, carbon materials‐COFs, polymer semiconductor‐COFs, COFs‐COFs heterojunction) summarized. Finally, challenges long‐term outlooks future offered terms efficiency, yield, stability, cost reaction mechanisms, well standardized evaluation method activities. It anticipated that this review can deliver new insights into fundamental engineering conversion, further accelerate development area.

Language: Английский

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